Mineral magic? Common mineral capable of making, breaking bonds

July 28, 2014

Reactions among minerals and organic compounds in hydrothermal environments are critical components of the Earth’s deep carbon cycle. They provide energy for the deep biosphere, and may have implications for the origins of life. However, very little is known about how minerals influence organic reactions. A team of researchers from Arizona State University have demonstrated how a common mineral acts as a catalyst for specific hydrothermal organic reactions – negating the need for toxic solvents or expensive reagents.

At the heart of organic chemistry, also known as carbon chemistry, is the covalent carbon-hydrogen bond (C-H bond) – a fundamental link between carbon and hydrogen atoms found in nearly every organic compound. gem-quality sphalerite in a quartz matrix Download Full Image

The essential ingredients controlling chemical reactions of organic compounds in hydrothermal systems are the organic molecules, hot pressurized water and minerals; but a mechanistic understanding of how minerals influence hydrothermal organic reactivity has been virtually nonexistent.

The ASU team set out to understand how different minerals affect hydrothermal organic reactions and found that a common sulfide mineral (ZnS, or Sphalerite) cleanly catalyzes a fundamental chemical reaction: the making and breaking of a C-H bond.

Their findings are published in the July 28 issue of the Proceedings of the National Academy of Sciences. The paper was written by a transdisciplinary team of ASU researchers that includes Jessie Shipp (2013 doctorate in chemistry and biochemistry), Ian Gould, Lynda Williams, Everett Shock and Hilairy Hartnett. The work was funded by the National Science Foundation.

“Typically you wouldn’t expect water and an organic hydrocarbon to react. If you place an alkane in water and add some mineral, it’s probably just going to sit there and do nothing,” explains Shipp. “But at high temperature and pressure, water behaves more like an organic solvent, the thermodynamics of reactions change and, suddenly, reactions that are impossible on the bench-top start becoming possible. And it’s all using naturally occurring components at conditions that can be found in past and present hydrothermal systems.”

A mineral in the mix

Previously, the team had found they could react organic molecules in hot, pressurized water to produce many different types of products, but reactions were slow and conversions low. This work, however, showed that in the presence of sphalerite, hydrothermal reaction rates increased dramatically, the reaction approached equilibrium and only one product formed. This very clean, very simple reaction was unexpected.

“We chose sphalerite because we had been working with iron sulfides and realized that we couldn’t isolate the effects of iron from the effects of sulfur. So we tried a mineral with sulfur, but not iron. Sphalerite is a common mineral in hydrothermal systems, so it was a pretty good choice. We really didn't expect it to behave so differently from the iron sulfides,” says Hartnett, an associate professor in the School of Earth and Space Exploration and the Department of Chemistry and Biochemistry in the College of Liberal Arts and Sciences at ASU.

This research provides information about exactly how the sphalerite mineral surface affects the breaking and making of the C-H bond. Sphalerite is present in marine hydrothermal systems (such as black smokers), and has been the focus of recent origins-of-life investigations.

For their experiments, the team needed high pressures (1,000 bar, or nearly 1,000 atm) and high temperatures (300 degrees Celsius) in a chemically inert container. To get these conditions, the reactants (sphalerite, water and an organic molecule) are welded into a pure gold capsule and placed in a pressure vessel, inside a furnace. When an experiment is done, the gold capsule is frozen in liquid nitrogen to stop the reaction, opened and allowed to thaw while submerged in dichloromethane to extract the organic products.

“This research is a unique collaboration because Dr. Gould is an organic chemist, and you combine him with Dr. Hartnett, who studies carbon cycles and environmental geochemistry, Dr. Shock, who thinks in terms of thermodynamics and about high temperature environments, and Dr. Williams, who is the mineral expert, and you get a diverse set of brains thinking about the same problems,” says Shipp.

Hydrothermal organic reactions affect the formation, degradation and composition of petroleum, and provide energy and carbon sources for microbial communities in deep sedimentary systems. The results have implications for the carbon cycle, astrobiology, prebiotic organic chemistry and, perhaps even more importantly, for "Green Chemistry," a philosophy that encourages the design of products and processes that minimize the use and generation of hazardous substances.

“This C-H bond activation is a fundamental step that is ultimately necessary to produce more complex molecules – in the environment those molecules could be food for the deep biosphere, or involved in the production of petroleum fuels,” says Hartnett. “The green chemistry side is potentially really cool since we can conduct reactions in just hot water with a common mineral that ordinarily would require expensive or toxic catalysts, or extremely harsh acidic or oxidizing conditions.”

Nikki Cassis

marketing and communications director, School of Earth and Space Exploration

ASU journalism students continue to accrue accolades

July 28, 2014

Students at the Walter Cronkite School of Journalism and Mass Communication at Arizona State University earned awards and recognition in reporting, photography and public relations, among other areas, for work done during the 2013-2014 academic year.

The accolades included national recognition from the Hearst Journalism Awards Program, The Associated Press, Investigative Reporters and Editors and the National Academy of Television Arts & Sciences. ASU students working on Cronkite Newswatch Download Full Image

“We are extremely proud of the outstanding work of our exceptional students,” said Cronkite School Associate Dean Kristin Gilger. “Year after year, our students are among the best in the country in national and regional journalism award contests – testifying to the dedication of our phenomenal students and faculty.”

Hearst Journalism Awards

For the 13th consecutive year, the Cronkite School finished in the top 10 nationally at the prestigious Hearst Journalism Awards. Cronkite secured sixth overall in the national contest based on student work in a variety of categories, including multimedia, television, radio, print and photojournalism.

Cronkite School students placed second in the Hearst broadcast category and fourth in writing. Individually, several students received notable recognition. Cronkite student Shayne Dwyer finished fourth in TV news reporting and traveled to the annual Hearst National Championships in Washington, D.C., where he won the television broadcast news championship.

Connor Radnovich was one of two students in the 2013-2014 competition to place in the top 10 in three separate categories – personality/profile writing, breaking news and photojournalism picture story/series.

Other top students included Molly J. Smith, fourth place for feature writing; Erin O’Connor, fifth place for multimedia news; Robby Baker, sixth place for TV feature reporting; Mark Remillard, seventh place for radio feature reporting; David Robles, eighth place for enterprise reporting; Cooper Rummell, ninth place for radio feature reporting; and Yihyun Jeong and Laura Sposato, ninth place for multimedia team reporting.

Rocky Mountain Emmys

Cronkite NewsWatch, the school’s student-produced television newscast, was recognized as the best student newscast at the 2013 Rocky Mountain Emmy Awards. The National Academy of Television Arts & Sciences recognized NewsWatch for an April 2013 broadcast covering immigration reform and the dangers of online donation scams. This is the third consecutive year NewsWatch has won best student newscast in the nation.

Kim Pestalozzi also won a Rocky Mountain Emmy in the student sports category for her story on a high school wrestler who overcame significant odds to achieve greatness. “Overcoming the Odds” aired on “Sports Watch 101” on FOX Sports Arizona. Cronkite NewsWatch is a 30-minute newscast produced by advanced broadcast students that reaches 1.9 million homes on Eight, Arizona PBS four days a week.

Investigative Reporters and Editors Awards

Carnegie-Knight News21 was a finalist in the Investigative Reporters and Editors Awards for outstanding student investigative work for a project examining the enduring battles facing post-9/11 veterans as they return home from war.

Top journalism students from across the country participated in the Carnegie-Knight News21 program, creating a multimedia project with dozens of stories, videos and photos that documented veterans as they navigate a federal bureaucracy ill-equipped to help them. ASU students Caitlin Cruz, Chad Garland, Peter Haden, Trahern Wallace Jones, Andrew Knochel, Rachel Leingang, Kay Miller, Mary Shinn, Jake Stein and Mauro Whiteman worked on the project, which was featured by national news organizations such as The Washington Post, NBCnews.com and the Center for Public Integrity.

AP Television and Radio Association Regional Awards

Cooper Rummell secured second place in the best use of sound category at the annual AP Television and Radio Association Regional Awards. Rummell was recognized for his KTAR radio story on “Maricopa County Jail Flags,” which examined Maricopa County Sheriff Joe Arpaio’s penalties for inmates who deface American flags in their jail cells.

The annual AP Regional Awards represent the highest standards of professional broadcast journalism across 13 states, including Arizona.

Arizona Photojournalism Awards

Jessie Wardarski was named the Arizona Press Club’s College Photographer of the Year at the Arizona Photojournalism Awards for her captivating photos of skydivers and farming. The awards program also honors professional still and video photography in categories ranging from news to sports. Wardarski’s award, which recognizes a portfolio of her work, includes a $1,000 scholarship.

The Arizona Press Club is a nonprofit organization of professional reporters, editors, photographers and designers from publications across the state.

Accolade Awards

The Cronkite School’s Public Relations Lab won seven awards in the Accolade Competition, an awards program for new media, film, television and videography.

The PR Lab took home an Award of Excellence for public service programming and two Awards of Merit for contemporary issues/awareness raising and editing for their “Be Bold. Be Strong. Be Able/ABIL.” campaign for the Arizona Bridge to Independent Living. Annie Carson, Montserrat Camacho, Nora Merza, Michelle Rivas and Morgan Theys contributed to the project.

The PR Lab also won an Award of Excellence in content/message delivery, and an Award of Merit in script/writing for the “Where Lives Touch” campaign for the National Newspaper Association. Abby Dugan, Cristina Peralta, Alex Lancial and Kyleigh Zmijewski developed a public service announcement. Kara Burns, Valerie Nunez, Victoria Stangl and Emily Wininger developed a website and infographics, and also conducted social media outreach for the campaign.

For their work for the Arizona Broadcasters Association, the PR Lab secured an Award of Merit in public service programming for a public service announcement titled “Inform. Inspire. Insight.” Jessica Choi, Alexa Chrisbacher, Kelsey Pfeffer, Kayla Pologa and Joshua Skalniak won the award. The Public Relations Lab is a full-service public relations agency at the Cronkite School that puts students to work creating communications campaigns and strategies for professional clients.

The PR Lab also took home an Award of Merit in public service programming for a campaign for the Tempe Coalition to eliminate marijuana use among adolescents. Jennifer Borbon, Zander Buel, Hannah Lurie and Leila O'Hara did production work on a PSA. Marlee Bever, Wahida Ifat, Steven Kapoloma, Ashley Provenzano and Torunn Sinclair worked on the script, concepts and initial shooting of the PSA.

GOT OUTCOMES! Coalition of Excellence Awards

Cronkite Public Relations Lab students won a GOT OUTCOMES! Coalition of Excellence Award for their Tempe Coalition campaign to reduce underage drinking. The winning campaign by Cassidy Olson, Rachel Steingard and Samantha Womer included outreach at community events, a pledge program, PSAs and billboards for the Tempe Coalition, an organization working to reduce drug use and underage drinking.

The GOT OUTCOMES! Coalition of Excellence Award is sponsored by the Community Anti-Drug Coalitions of America, a national organization committed to building drug-free communities.

Biotech University

Rachel Lund received top honors at the 2014 Biotech University contest. Lund captured the grand prize, an all-expenses-paid trip to Australia for her winning entry, “Milk in America.” For her entry, she produced a radio segment exploring how genetically modified organisms can be an affordable solution to feeding the world’s population.

Biotech University is a one-day spring seminar that introduces journalism students from across the country to the emerging science of biotechnology.

Global Editors Network Hackdays

Thania Betancourt, Sachit Dhal and Mauro Whiteman were part of a select group of college students who competed against professional news organizations in the Global Editors Network Hackdays, a worldwide competition that addresses the need for more collaborative innovation in newsrooms by generating new ideas and best practices.

The Cronkite team, one of only two colleges in the 13-team field, engaged in the November 2013 competition at Yahoo’s headquarters in Sunnyvale, California. The field included professional news organizations such as CNN, the Los Angeles Times and the Chicago Tribune. The judges commended the Cronkite team’s creativity and execution.

McCain Institute Sedona Forum

Torunn Sinclair and Hannah Lurie were selected to participate at the prestigious Sedona Forum hosted by the McCain Institute for International Leadership at ASU. The Sedona Forum brings together top government and private sector leaders and issue experts to Sedona, Arizona, for focused discussion around some of the world’s most pressing challenges.

This year’s event included visits from former Secretary of State Hillary Clinton and former Deputy Secretary of State Bill Burns. Headquartered in the nation’s capital, the McCain Institute is a center for research and action in national security and foreign policy.

Reporter , ASU News